Method for reacting organic halides

ABSTRACT

A method for carrying out reactions of the Friedel-Crafts type, such as alkylation, acylation, polymerization, sulfonylation and dehydrohalogenation. The reactions are catalyzed by arene-metal tricarbonyl complexes and when the reaction vessel contains aromatic substrates the catalyst may be generated in situ from a metallic hexacarbonyl. The arene-metal tricarbonyl catalyst is more selective than conventionally employed Friedel-Craft catalysts in that it yields generally para isomers with little of the ortho variety and very little if any of the meta variety when the aromatic substrate is reacted with organic halide. It is also possible to form the arene-metal tricarbonyl catalyst outside of the reaction vessel and then proceed by adding it to the vessel containing the substrate and the organic halide as is the case with dehydrohalogenation reactions wherein there are no aromatic rings available, the substrate in that instance being aliphatic.

United States Patent [191 Farona et al.

[ METHOD FOR REACTING ORGANI HALIDES Ohio [73] Assignee: The University of Akron, Akron,

Ohio

[22] Filed: Mar. 9, 1973 [21] Appl. No.: 339,637

Related US. Application Data [63] Continuation-in-part of Ser. No. 119,908, March 1,

I971, abandoned.

[52] US. Cl 260/592, 260/47 R, 260/469, 260/543 R, 260/578, 260/59I, 260/590,

260/619 R, 260/620, 260/668 B, 260/671 R [51] Int. Cl. C070 49/76, C07C 49/82 [58] Field of Search 260/590, 592

[56] References Cited OTHER PUBLICATIONS Farona et al., .I. Am. Chem. Soc., 93, 2,826-2,827, (1971).

[ Aug. 27, 1974 Primary ExaminerDaniel D. Horwitz Attorney, Agent, or FirmHamilton, Renner & Kenner ABSTRACT A method for carrying out reactions of the Friedel- Crafts type, such as alkylation, acylation, polymerization, sulfonylation and dehydrohalogenation. The reactions are catalyzed by arene-metal tricarbonyl complexes and when the reaction vessel contains aromatic substrates the catalyst may be generated in situ from a metallic hexacarbonyl. The arene-metal tricarbonyl catalyst is more selective than conventionally employed Friedel-Craft catalysts in that it yields generally para isomers with little of the ortho variety and very little if any of the meta variety when the aromatic substrate is reacted with organic halide. It is also possible to form the arene-metal tricarbonyl catalyst outside of the reaction vessel and then proceed by adding it to the vessel containing the substrate and the organic halide as is the case with dehydrohalogenation reactions wherein there are no aromatic rings available. the substrate 'in that instance being aliphatic.

18 Claims, N0 Drawings METHOD FOR REACTING ORGANIC HALIDES CROSS REFERENCE TO RELATED APPLICATION This application is a continuation-in-part application fU.S. Ser. No. 119,908, filed Mar. 1, 1971, now abandoned.

BACKGROUND OF THE INVENTION Substitution of halogens from organic compounds by other organic groups or the mere removal of halogens, without substitution, to form new organic compounds is well known by a variety of standard name reactions. The Fn'edel-Crafts type of reactions, usually carried out by the catalyst aluminum trichloride, are an example.

The reactivity of the arena-metal tricarbonyl complexes has also been examined and it is known that the tricarbonylchlorobenzenechromium complex will enter into a nucleophilic reaction with methyl alcohol to form the anisole complex. Further, electrophilic reactions are also facilitated such as Friedel-Crafts acetylation of the tricarbonyl-benzene chromium complex withacetyl chloride in the presence of aluminum trichloride. Both types of reaction yield a product which retains the arene-metal tricarbonyl complex.

SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide a method for reacting organic halides in alkylations, acylations, polymerizations, sulfonylations and dehydrohalogenations.

It is another object of the present invention to provide a method for carrying out these reactions in the presence of an arene-metal tricarbonyl catalyst.

It is a further object of the present invention to employ a catalyst which is easier to use, with respect to storage and handling, in that the catalyst may be generated in solution within the reaction vessel or without the reaction vessel and subsequently added thereto.

It is yet another object of the present invention to employ a catalyst which promotes attack on the aromatic ring generally at the para position rather than at the ortho position and usually excludes attack at the meta position.

These and other objects of the invention, and the advantages thereof, will be apparent in view of the detailed disclosure of the invention as set forth below.

In general, it has now been found that an organic halide RX, and an arene-metal tricarbonyl represented by the general formula,

DESCRIPTION OF THE PREFERRED EMBODIMENTS- The catalyst may be prepared in advance of a catalysis reaction according to the reaction mechanism M(CO):4

where R is selected from the class consisting of electron donating and ring activating groups such as hydrogen, alkyl groups having from one to about six carbon atoms, alkoxide groups having from one to about four carbon atoms, aryl and aryloxide groups having from six to about 12 carbon atoms including alkyl substituents, amino and hydroxide. The metal, M, is selected from the group consisting of Cr, Mo, and W with molybdenum being preferred.

Representative alkyl groups include methyl, ethyl, isopropyl, t-butyl, pentyl, hexamethyl and the like. Representative alkoxide groups include methoxy, ethoxy, propoxy, butoxy, sec-butoxy and the like.

Representative aryl groups include phenyl, naphthyl and the phenyl ring with substituted alkyl groups such as methyl, ethyl, propyl, butyl, sec-butyl, pentyl, 2-

pentyl, hexamethyl and the like. A representative aryloxide is diphenyl ether.

R may further be selected from the class consisting of ring deactivating and electron withdrawing groups such as the halides, the haloalkyls, the alkylbenzoate esters, the aldehydes and sulfonyl halides, particularly sulfonyl chloride. Representative halides are fluoro, chloro and bromo, and representative alkylbenzoate esters are those having from one to three carbon atoms such as methyl benzoate, ethyl benzoate, propyl benzoate and isopropyl benzoate. Representative aldehydes are those having from one to four carbon atoms. Representative haloalkyl groups include methyl bromide, methyl chloride and methyl fluoride.

In addition to the aforementioned mono-substituted phenyl compounds which may be utilized it is also possible to select poly-substituted phenyl compounds having up to five substituent groups. The generic formula for such a compound may be expressed as follows:

R! I I I I R R m3 wherein R may be the same as any of the aforementioned R groups including hydrogen. As will be obvious to one skilled in the art, a large number of the existing polysubstituted phenyl compounds can thus be used in accordance with the teaching of this pioneer invention. Since it would be impractical to provide an all inclusive listing, only some of the representative compounds according to formula F(3) will be set forth.

Representative compounds wherein one or more of the R groups are other than hydrogen include anisole, chlorobenzene, benzyl chloride, benzyl fluoride, phenol, toluene, t-butyl benzene, o,m and pdichlorobenzene, diphenyl ether, biphenyl, o,m zmd pxylene, p-toluene sulfonyl chloride, methyl benzoate, ethyl benzoate, propyl benzoate, isopropyl benzoate, 2,3-dimethoxyaniline, 2,4-dihydroxytoluene, 3,4- dimethoxytoluene, 4-hydroxy-3-methoxytoluene,

3 1,2,4,5-tetramethylbenzene, 3,4,5-trihydroxytoluene and l,3-dihydroxy-4,5,6-trimethylbenzene.

Selection of any specific aromatic compound will of course be dependent upon factors such as the product desired and the availability or existence of the compound. A person skilled in the art will generally know numerous existing compounds. Moreover, as to other compounds, any standard reference book, such as the CRC Handbook of Chemistry and Physics, could be consulted thus enabling the skilled artisan to obtain readily the names of other existing compounds.

Preparation of the catalyst according to F(2) is necessarily precedent to a catalysis reaction when aryl radicals are neither present nor constituents of the reactants chosen to form the product compounds. Thus, in the case of dehydrohalogenation reactions, the catalyst will promote the formation of the olefin, but it must be prepared in advance as there are no aromatic rings available in the reaction vessel.

Thus, a utility of the present invention is that this catalyst may be generated during the catalysis reaction. Thus, when the metal hexacarbonyl and a substrate reactant having an or acyl radical constituent are brought together in a reaction vessel, the arene-metal tricarbonyl catalyst will be generated in situ. Upon the addition of the desired organic halide, the particular reaction, e.g., alkylation, acylation, polymerization, sulfonylation, will then proceed to form the desired products.

According to the method of the present invention, aromatic substrates are combined with organic halides, having the generic formula RX, in the reaction vessel. The catalyst removes the halogen forming a highly reactive carbonium ion on the organic moiety R. Subsequent attack by the carbonium ion upon the substrate molecule yields a product, resulting from the attachment of the organic radical R to the substrate, and a hydrogen ion. The hydrogen ion quickly removes the halogen with at least partial regeneration of the catalyst. ln this manner alkylations, acylations, polymerizations and sulfonylations occur. Of course, the catalyst also promotes dehydrohalogenation. However, since there is no aromatic substrate the catalyst merely removes the halogen from the organic halide to yield an olefin.

The organic halide RX, wherein X is generally selected from bromine, chlorine and fluorine, will be chosen according to the desired reaction, e.g., alkyl, aryl or acyl substituted phenyl halides for alkylation and acylation, sulfonyl halides for sulfonylation and polymerization and alkyl halides for dehydrohalogenation. The organo group, or R, may therefore be selected from the class consisting of alkyl radicals having from one to about carbon atoms, aryl radicals having from six to about l2 carbon atoms. Alkoxide radicals having from one to about four carbon atoms and aldehydes having from one to about four carbon atoms, and haloalkyl groups such as methyl bromide, methyl chloride and methyl fluoride may also be used in the copolymerization reaction. When aryl radicals having alkyl substituents are utilized for the alkylation and polymerization reactions it is necessary for the halogen to be bonded to the substituent rather than the ring inasmuch as the catalyst removes, for instance, chlorine much more readily from benzyl chloride than from chlorobenzene.

Representative alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl. heptyl, octyl, nonyl, decyl isomers thereof and the like. Representative aryl radi cals include tolyl, xylyl, methyl naphthyl and the like.

Furthermore, when selecting the xylenes, dihalo compounds may be utilized as the .catalyst can readily remove both halogens from their methyl partner. As before, the skilled artisan can refer to a reference handbook to ascertain the existing organic halides which he may desire to react.

Whether the catalyst is prepared within the reaction vessel by reacting molybdenum hexacarbonyl with the aromatic substrate, or it is separately prepared and added, the reactants are all placed within the reaction vessel. Generally, the reactants are soluble within the substrate; however, if such is not the case, the reaction may be carried out in heptane or any other saturated liquid hydrocarbon or any aryl such as benzene or substituted benzene. The reaction is preferably carried out in an inert atmosphere such as nitrogen. In order to generally initiate the reaction, the vessel is usually fitted with a reflux condenser and heated from ambient temperatures through a temperature range of a few degrees to approximately C, depending upon the type of reaction and the reactants. Reaction time is also dependent upon the latter factors and accordingly ranges from about one hour to about 36 hours or longer. During this time it is necessary to keep the reactants mixed which may be readily accomplished with a conventional magnetic stirrer or the like. Mechanisms for the various reactions are as follows:

An alkylation according to the present invention is thought to proceed according to the following reaction mechanism;

where R is an alkyl or aryl group as noted above and R is hydrogen, alkyl, alkoxide, sulfonyl chloride, hydroxide, aryl or aryl oxide as noted above and M is a metal from the group, Cr, Mo and W, and X is a halogen from the group of Br, Cl and F. The catalyst is formed in the reaction vessel from part of the aromatic substrate reactant or it may be added in its active form whereby Step I is omitted. In Step 2. it proceeds to remove the halogen from the organic halide, RX, resulting in the formation of a highly reactive carbonium ion, R", which subsequently attacks the remaining part of the aromatic substrate, as in Step 3, with concurrent release of a hydrogen ion. In Step 4, the hydrogen ion removes the halogen and the catalyst is regenerated.

An acylation according to the present invention is thought to proceed according to the following reaction mechanism;

where R is an alkyl or aryl group as noted above and R is hydrogen, alkyl, alkoxide or hydroxide, aryl aryloxide as noted above and M is a metal from the group Cr, Mo and W,

and X is a halogen from the group of Br, Cl and F. The catalyst is again formed in Step 1, as described before or merely added directly to the reactants. In Step 2 it proceeds to remove the halogen from the organic acid halide resulting in the formation of a highly reactive acyl cation RC =O, which subsequently attacks the aromatic substrate reactant, as in Step 3, with concurrent release of a hydrogen ion. In Step 4, the hydrogen ion removes the halogen and the catalyst is regenerated.

Two types of polymers may be produced according to the present invention. A branched structure may be formed by the polymerization of one monomeric substance or the combination of two monomers. A linear polymer may be produced by selecting an aryl substrate, A. having only two positions subject to carbonium ion attack and having ligzmds at each of the other positions relatively unsusceptible to carbonium ion attack. The organic halide selected, B, is a dihalocompound such that carbonium ions may form at two ing to the present invention is thought to proceed ac-- cording to the following reaction mechanism;

where R is an aryl radical as noted above and R is alkyl, alkoxide, or haloalkyl as noted above, and M is a metal from the group Cr, Mo and W, and X is a halogen from the group of Br, Cl and F. The organic halide has an aryl ring, and therefore will react with molybdenum hexacarbonyl as in Step 1, or if desired, the active form of the catalyst may be prepared separately and added to the monomeric halide R-R-X as in Step 2 where the halogen is removed resulting in the formation of a highly reactive carbonium ion, R-R' which subsequently attacks the organic halide as in Step 3, with concurrent release of a hydrogen ion. The catalyst is again regenerated as by Step 4. The reaction generally proceeds with substantial conversion of the monomer to the dimer R-R'-R-R-X; then loss of the halogen again results in a carbonium ion which combines in a repetitive process to produce a' polymer having an average number molecular weight ranging from approximately 5,000 to 30,000. Owing to the reactive sites of a phenyl ring, 0, m, and p, to they ligand R, the polymer is highly branched.

Polymerization to form a linear copolymer according to the present invention is thought to proceed according to the following reaction mechanism:

where R is alkyl, alkoxide, or hydroxide as noted above and R is alkyl, alkoxide, aldehyde, sulfonyl or haloalas noted above,

and M is a metal from the group Cr, Mo and W,

and X is a halogen from the group of Br, Cl and F.

Removal of both halides from the dihalo-compound produces two reactive carbonium ions which will combine with the available positions of the aromatic substrate compound in a repetitive process to form a linear copolymer of average number molecular weight ranging between 5,000 and 30,000.

A sulfonylation according to the present invention is thought to proceed according to the following reaction mechanism:

where R is an alkyl or aryl group as noted above and R is hydrogen, alkyl, alkoxide, aryl, aryloxide or hydroxide as noted above and M is a metal from the group Cr, Mo and W,

and X is a halogen from the group of Br, Cl and F. The catalyst is again formed in Step 1, as described before or merely added directly to the reactants. in Step 2 it proceeds to remove the halogen from the sulfonyl halide, R-SO -X, resulting in the formation of a highly reactive sulfonium ion. R-SO which subsequently attacks the aromatic substrate reactant as in Step 3, with concurrent release ota hydrogen ion. ln Step 4. the hydrogen ion removes the halogen and the catalyst is regenerated.

A dehydrohalogenation according to the present invention is thought to proceed according to the following reaction mechanism:

Step 1 where R is an alkyl group as noted above and R is hydrogen, alkyl, alkoxide, sulfonyl chloride,

amino, aryl and aryloxide, halide, hydroxide and alkylbenzoate esters as noted above and M is a metal from the group Cr, Mo and W,

and X is a halogen from the group of Br, Cl and F. In this reaction it is desirable to form the active catalyst apart from the reactants since M(CO) will not combine with an alkyl halide and if an aryl halide is present some alkylation will occur. In Step 1, the catalyst removes the halogen from the alkyl halide, R-X, resulting in the formation of a highly reactive carbonium ion. R". With subsequent loss of a hydrogen ion, as in Step 2, an alkene product is formed. In Step 3, the hydrogen ion removes the halogen and the catalyst is regenerated.

The invention will be more fully understood by reference to the following examples which describe the various types of reactions.

EXAMPLE I An aikylation of an aryl compound is promoted by the combination of 12.2 gms. of phenol; 20 cc. of tbutyl chloride; and 50 mg. of molybdenum hexacarbonyl in 120 cc. of the solvent heptane. These reactants are placed in a suitable vessel and mixed as by a magnetic stirring apparatus. The vessel is fitted with a reflux condenser and is then heated, to approximately 98C. for l8 to 24 hours. At the end of this time period, the desired product is separated by suitable means well known to one skilled in the art.

combination of 125 cc. of anisole; 4 cc. of acetyl chloride and 2550 mg. of molybdenum hexacarbonyl.

These reactants are placed in a suitable vessel, and 5 thoroughly mixed while refluxing at approximately 100C. for 36 hours. At the end of this time period, the desired product is separated by suitable means.

EXAMPLE Ill A polymerization of an organic halide to fonn a branched polymer is promoted by the combination of 100 gms. of benzyl chloride with 50 mg. of molybdenum hexacarbonyl. The compounds are placed in a suitable vessel, mixed and refluxed at approximately 100C. for 1 hour. At the end of this time period, the branched polymer is separated by suitable means.

EXAMPLE IV A linear polymer may be formed by combining 7.3

EXAMPLE V the end of this time period, the desired product is separated by suitable means.

EXAMPLE V1 A debydrohalogenation of an organic halide is promoted by the combination of 100 cc. of t-butyl chloride with 200 mg. of toluene molybdenum tricarbonyl. The compounds are placed in a suitable vessel, mixed and refluxed at approximately 51C. for 4 hours. At the end 10 of this time period the desired product is separated by suitable means.

The results of these and similar reactions have been set forth in Tables 15 below. In Table 1, examples 1-10 represent alkylations. In Table 2, examples 1-6 represent acylations. In Table 3, example 1 represents formation of a linear polymer and examples 2-3 represent formation of branched polymers and 45 represent branched or linear polymers. In Table 4, examples 1-3 represent sulfonylations. In Table 5, example 1, a dehydrohalogenation reaction was attempted without the arene metal tricarbonyl catalyst and no reaction was evidenced. 1n example 2, the catalyst was present, being first prepared as in F(2) above, and the alkene, isobutylene, was quickly formed thereby. Although the product may be isolated, by continuing the reaction, the polymeric products which are known to occur when isobutyl cations attack isobutylene are prepared.

Thus, it can be seen that the disclosed invention carries out the objects of the invention set forth above.

A sulfonylation ofan arylsulfonyl halide is promoted As will be apparent to those skilled in the art, many by combining 160 cc. of toluene; 3.8 gms. of p-tosyl chloride and 25 to mg. of molybdenum hexacarbonyl in a suitable vessel. The reactants are then mixed and refluxed at approximately 110C. for 36 hours. At

modifications can be made without departing from the spirit of the invention herein disclosed and described, the scope of the invention being limited solely by the scope of the attached claims.

Table 1 Alkylation Reactions Aromatic Organic Added Reaction Substrate Halide Catalyst Conditions Yield Comments 1. Toluene t-butyl chloride Mo(CO) Reflux 17.9 g Exclusively para (100 ml) (12.6 g) (0.20 g) 5 hr 88% substitution 2. Toluene t-butyl chloride To1Mo(CO) Reflux 16.7 g (100 ml) (12.6 g) (0.20 g) l hr 81.8% 3. Toluene Cyclohexyl Mo(CO),; Reflux 19.7 g (160 ml) chloride (10 g) (0.05 g) 6 hr 84.5% 4. Toluene Benzyl Mo(CO), Reflux 16.4'g 100% alkylation, 10%

(200 ml) chloride (12.6 g) (0.03 g) 12 hr 90% polymer, 90% totylphcnylmethane 5. Toluene n-propyl chloride To1Mo(CO) 130 7.8 g Carried out in glass- (50 ml) (8.9 g) (0.20 g) 6 hr 50.5% lined Parr bomb, product exclusively pcymene 6. t-butyl n-ehloroheptane Mo(CO),, 140 Only secondary benzene (8.8 g) (0.01 g) 24 hr alkylates obtained m1) 7. Toluene Cyclohexyl To1Mo(CO) Reflux 12.8 g ml) fluoride (11.2 g) (0.1 g) 6 hr 67.3% 8. Toluene Cyclohexyl To1Mo(CO) Reflux 6.7 g Extensive catalyst ml) bromide (26.4 g) (0.1 g) 8 hr 23.4% decomposition 9. Anisole t-butyl chloride Mo(CO) 9.5 g

ml) 6.8 g) 0.03 g 24 hr 79% 10. Phenol t-butyl chloride Mo(CO),, Reflux 18.8 g 120 m1 heptane solvent.

- 12.0 g) (0.01 g) 18 hr 96% 93% p-t-butylphenol, 3%

2,6-di-tbutylpheno1 Table 2 Acylation Reactions Aromatic Organic Added Reaction Substrate Halide Catalyst Conditions Yield Comments 1. Toulene Aeetyl Mo(CO), Reflux 1.2 g Only p-methyl aceto- (100 ml) chloride (7.8 g) (0.15 g) 24 hr 9% phenone isolated 2. Toulene Propionyl Mo(CO),, Reflux 1.85 g Only para ucylation m1) chloride 6.35 g) (0.05 g) 24 hr 18% obtained 3. Toluene Benzoyl chloride Mo(CO), Reflux 2.5g Only p-methyl (160 ml) 6.05 g) (0.15 g) 18 hr 29.7% benzophenone isolated Table 2 Continued Acylation Reactions Aromatic Organic Added Reaction Substrate Halide Catalyst Conditions Yield Comments 4. Toluene Benzoyl chloride TolMo(CO);1 Reflux 5.65 g Same product as 3 (160 ml) 6.05 g) (0.02 g) 12 hr 67% 5. Anisole Acctyl chloride MO(C )|i 100 10.2 g p-methoxyaceto 125 ml) 7.8 g) (0.02 g) 36 hr 68% phcnone. 4% o-methoxyacctophenone 6. Anisole Benzoyl chloride TolMo(CO) 7.4 g Only p-methoxybenzo- 150 m1) (7.0 g (0.15 g) 18 hr 70% phcnone isolated Table 3 Polymerization Reactions Aromatic Organic Added Reaction Substrate Halide Catalyst Conditions Yield Comments 1. Durene p-xylylcne- Mo(CO) 1 10 9.6 g Copolymer nearly insoluble dichloride 0.01 g 3 hr (98%) in common organic solvents 2. Benzyl Mo(CO) 1 10 100% chloride (0.1 g) l hr (neat) 3. Benzyl TolMo(CO); 140 100% fluoride (neat) 4. Diphenyl Benzene-1,3-di- Mo(CO) 1 10 1.4 g Tan-colored copolymer ether sulfonylchloride (0.1 g) 3 hr 22% g g) 5. Diphenyl Benzene-1.3di- TolMo(CO) 2.1 g Same as 4.

ether sulfonylchloride (0.1 g) 3 hr 32 (2.6 g) (4.3 g)

Table 4 Sulfonylation Reactions Aromatic Organic Added Reaction Substrate Halide Catalyst Conditions Yield Comments 1. Toluene Tosyl chloride Mo(CO) Reflux 2.1 g Product is 4,4- (160 ml) (3.8 g) (0.02 g) 36 hr 43% ditolylsulfone 2. Anisole Tosyl chloride Mo(CO) 1.15 g Product is 4-methylml) (3.8 g) (0.02 g) 24 hr 22% 4'-methoxydiphenylsulfonc 3. Anisole Tosyl chloride TolMo(CO):, 115 1.3 g Same as 2 (160 ml) (3.8 g) (0.03 g) 18 hr 25% Table 5 Dehydrohalogenation Reaction Aromatic Organic Added Reaction Substrate Halide Catalyst Conditions Yield Comments 1. Lbutyl chloride MO(CO) reflux. 20 hr. none no reaction. 96% Mo(CO).;

recovered 2. t-butyl chloride Toluenereflux, 4 hr. large amounts of HCI evolved,

( 100 ml) Mo(CO);, 2 polymeric substances (200 mg) obtained What is claimed is: about 12 carbon atoms including alkyl substituents and 1. The process of reacting an organic acyl halide with hydroxide, reacting said metallic hexacarbonyl com an aromatic substrate to form an aromatic product pound with part of said aromatic substrate to yield an comprising the steps of: charging a reaction vessel with arene metal tricarbonyl catalyst having the formula a metallic hexacarbonyl compound having the formula l o I I M(CO) wherein M is selected from the group consist- R ing of Cr, Mo and W, adding an aromatic substrate hav 0 ing the formula R! R! R! R! C O )a R T charging thte reaction vessel with an organic acyl halide havin the orrnula wherein R is selected from the group consisting of hy- 65 g drogen, alkyl groups having from 1 to about 6 carbon atoms, alkoxide groups having from 1 to about 4 carbon atoms, aryl and aryloxide groups having from 6 to x wherein R is an alkyl group having from one to about carbon atoms, and X is'selected from the group consisting of bromine, chlorine and fluorine, heating said reaction vessel from ambient temperatures to a temperature sufficient to cause said catalyst to remove the halide from said organic halide with generation of an acyl cation so that said acyl cation will attack the remaining part of said aromatic substrate to yield the aromatic product.

2. The process as in claim 1, wherein said acyl cation is formed in a temperature range from a few degrees above said ambient temperature to about l35C.

3. The process as in claim 1, wherein said reaction is carried out in an inert atmosphere.

4. The process as in claim 3, wherein said inert atmosphere is nitrogen.

5. The process as in claim 1, wherein said reaction is carried out in a solvent selected from the group consisting of a saturated liquid hydrocarbon and liquid aryl compounds.

6. The process as in claim 1, wherein said organic alkyl halides are selected from the group consisting of acetyl chloride, and propionyl chloride.

7. The process as in claim 1, wherein said aromatic substrate is selected from the group consisting of toluene, and, anisole.

8. The process as in claim 1, wherein the metal of said arene metal tri-carbonyl catalyst is molybdenum and where the R constituent of said catalyst is selected from the group consisting of methyl and methoxy radicals.

9. The process of reacting an organic acyl halide in the presence of an arene metal tricarbonyl catalyst with an aromatic substrate to form an aromatic product comprising the steps of: charging a reaction vessel with an organic acyl halide having the fonnula wherein R is an alkyl group having from one to about 20 carbon atoms, and X is selected from the group consisting of bromine, chlorine and fluorine, adding an aromatic substrate having the fonnula M(CO)3 wherein R" is selected from the group consisting of hydrogen. alkyl groups having from one to about six carbon atoms. alkoxide groups having from one to about four carbon atoms, aryl and aryloxide groups having from six to about l2 carbon atoms including alkyl substituents, amino, halide, alkylbenzoate esters having from one to three carbon atoms, sulfonyl chloride and hydroxide, and M is selected from the group consisting of Cr, Mo, and W, heating said reaction vessel from ambient temperatures to a temperature sufficient to cause said catalyst to remove the halide from said organic halide with generation of an acyl cation from said organic halide so that said acyl cation will attack said aromatic substrate to yield the aromatic product.

10. The process of reacting an organic acyl halide with an aromatic substrate to form an aromatic product comprising the steps of: charging a reaction vessel with a metallic hexacarbonyl compound having the formula M(CO) wherein M is selected from the group consisting of Cr, Mo and W, adding an aromatic substrate having the formula wherein R is selected from the group consisting of hydrogen and alkyl groups having from one to about six carbon atoms, reacting said metallic hexacarbonyl compound with part of said aromatic substrate to yield an arene metal tricarbonyl catalyst having the formula charging the reaction vessel with an organic acyl halide having the formula wherein R is selected from the group consisting of an alkyl group having from one to about20 carbon atoms and X is selected from the group consisting of bromine, chlorine and fluorine, heating said reaction vessel from ambient temperatures to a temperature sufficient to cause said catalyst to remove the halide from said organic halide with generation of an acyl cation from said organic halide so that said acyl cation will attack the remaining part of said aromatic substrate to yield the aromatic product.

11. The process as in claim 10, wherein said acyl cation is formed in a temperature range from a few degrees above said ambient temperature to about C.

12. The process as in claim 10, wherein said reaction is carried out in an inert atmosphere.

13. The process as in claim 12, wherein said inert atmosphere is nitrogen.

14. The process as in claim 10, wherein said reaction is carried out in a solvent selected from the group consisting of a saturated liquid hydrocarbon and liquid aryl compounds.

15. The process as in claim 10, wherein said organic acyl alkyl halides are selected from the group consisting of acetyl chloride, and propionyl chloride.

16. The process as in claim 10, wherein said aromatic substrate is toluene.

wherein R is selected from the group consisting of an alkyl group having for one to about carbon atoms and X is selected from the group consisting of bromine, chlorine and fluorine, adding an aromatic substrate having the formula I R! wherein R is selected from the group consisting of hydrogen and alkyl groups having from one to about six carbon atoms, adding an arene metal tricarbonyl catalyst having the formula wherein R" is selected from the group consisting of hydrogen, alkyl groups having from one to about six carbon atoms, alkoxide groups having from one to about four carbon atoms, aryl and aryloxide groups having from six to about 12 carbon atoms including alkyl substituents, amino, halide, alkylbenzoate esters having from one to three carbon atoms, sulfonyl chloride and hydroxide, and M is selected from the group consisting of Cr, Mo, and W, heating said reaction vessel from ambient temperatures to a temperature sufficient to cause said catalyst to remove the halide from said organic halide with generation of an acyl cation from said organic halide so that said acyl cation will attack said aromatic substrate to yield the aromatic product.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3 832 403 Dated August 27 1974 Inventor). Michael F. F arona et a1 I It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 3, line 47, delete "substitutedwphenyl". Column 13,-

line 22, before the first word "alkyl" insert acyl Column 14, line 20, delete the two dashes after the formula.

Signed and sealed this 7 th day of' January 1975.

I'IcCOY 1. GIBSON JR.

Commissioner of Patents Attesting Officer USCOMM-DC OOS'IO-PGQ FORM P0-1050(10-69) I 1 I u.s., eo'vznuuzmmmmus OFFICE 93o 

2. The process as in claim 1, wherein said acyl cation is formed in a temperature range from a few degrees above said ambient temperature to about 135*C.
 3. The process as in claim 1, wherein said reaction is carried out in an inert atmosphere.
 4. The process as in claim 3, wherein said inert atmosphere is nitrogen.
 5. The process as in claim 1, wherein said reaction is carried out in a solvent selected from the group consisting of a saturated liquid hydrocarbon and liquid aryl compounds.
 6. The process as in claim 1, wherein said organic alkyl halides are selected from the group consisting of acetyl chloride, and propionyl chloride.
 7. The process as in claim 1, wherein said aromatic substrate is selected from the group consisting of toluene, and, anisole.
 8. The process as in claim 1, wherein the metal of said arene metal tri-carbonyl catalyst is molybdenum and where the R'' constituent of said catalyst is selected from the group consisting of methyl and methoxy radicals.
 9. The process of reacting an organic acyl halide in the presence of an arene metal tricarbonyl catalyst with an aromatic substrate to form an aromatic product comprising the steps of: charging a reaction vessel with an organic acyl halide having the formula
 10. The process of reacting an organic acyl halide with an aromatic substrate to form an aromatic product comprising the steps of: charging a reaction vessel with a metallic hexacarbonyl compound having the formula M(CO)6 wherein M is selected from the group consisting of Cr, Mo and W, adding an aromatic substrate having the formula
 11. The process as in claim 10, wherein said acyl cation is formed in a temperature range from a few degrees above said ambient temperature to about 135*C.
 12. The process as in claim 10, wherein said reaction is carried out in an inert atmosphere.
 13. The process as in claim 12, wherein said inert atmosphere is nitrogen.
 14. The process as in claim 10, wherein said reaction is carried out in a solvent selected from the group consisting of a saturated liquid hydrocarbon and liquid aryl compounds.
 15. The process as in claim 10, wherein said organic acyl alkyl halides are selected from the group consisting of acetyl chloride, and propionyl chloride.
 16. The process as in claim 10, wherein said aromatic substrate is toluene.
 17. The process as in claim 10, wherein the metal of said arene metal tricarbonyl catalyst is molybdenum and where the R'' constituent of said catalyst is selected from the group consisting of methyl and methoxy radicals.
 18. The process of reacting an acyl organic halide in the presence of an arene metal tricarbonyl catalyst with an aromatic substrate to form an aromatic product comprising the steps of: charging a reaction vessel with an acyl organic halide having the formula 